Methylene diamine ester and method of making same



Patented July 21, 1942 UNITED STATES PATENT OFFICE METHYLENE DIAMINEESTER AND METHOD OF MAKING SAME Melvin De Groote, University City, andBernhard Keiser, Webster Groves, Mo., assignors to PetroliteCorporation, Ltd., Wilmington, Dei., a corporation of Delaware NoDrawing. Original application June 27, 1940,

Serial No. 342,730. Divided and this applicacan be included in the broadtion June 14, 1941, Serial No. 398,143

g Claims. This invention relates to a new composition of -matter, ourpresent application being a division of our parent application, SerialNo. 342,730, filed June 27, 1940, which resulted in U. S. Patent No.2,250,407, dated July 22, 1941.v I

The main object of our invention is to provide a new. material or newcomposition of matter, that is particularly adapted for use as ademulsifier in the resolution of crude oil emulsions, but which may beemployed in some other arts, hereinafter indicated, and may also haveadditional uses in other arts that we have not as yet investigated.

Another object of our invention is to provide a novel method for makingsaid new material or composition of matter.

The demulsifier or demulsifying agent that forms the subject-matter ofour present ap cation consists of a compound or mixture of compoundsthat comprises the esteriflcation product of a high molecular weightcarboxy acid or its equivalent and a hydroxylated tertiary methylene.diamine of the kind hereinafter described. Said compound or mixture ofcoin pounds is characterized by the presence of an acyl radical derivedfrom a suitable high molec-- ular weight carboxy acid of the kind whichwill be described in detail subsequent-1y.

In order that our invention may be clearly understood, we willhereinafter give several examples of chemical compounds embodying ourinvention; and we will explain how said compounds can be produced orobtained.

The expression higher molecular weight carboxy acids is an expressionfrequently employed to refer to certain organic acids, particularlymonocarboxy acids, having more than six carbon atoms, and generally lessthan 40 carbon atoms. The commonest examples include thedetergentforming acids, 1. e., those acids which combine with alkalis toproduce soap or soap-like bodies. The detergent-forming acids, in turn,include naturally-occurring fatty acids, resin acids, such as abieticacid, naturally-occurring petroleum acids, such as naphthenic acids, andcarboxy acids produced by the oxidation of petroleum.

A will be subsequently indicated, there are other acids which havesomewhat similar characteristics and are derived from somewhat differentsources and are different in structure, but

generic term previously indicated.

Among sources of such acids may be mentioned straight chain and branchedchain, saturated and unsaturated, carboxylic, aliphatic,

alicyclic, fatty, aromatic, hydroaromatic, and

ing, in addition to those mentioned, melissic acid, stearic acid, oleicacid, ricinoleic acid, diricinoleic acid, triricinoleic acid,polyricinoleic acid, ricinostearolic acid, ricinoleyl lactic acid,acetylricinoleic acid, chloracetyl-ricinoleic acid, linoleic acid,linolenic acid, lauric acid, myristic acid, undecylenic acid, palmiticacid, mixtures of any two or more of the above mentioned acids or otheracids, mixed higher fatty acids derived from animal or vegetablesources, for example, lard, cocoanut oil, rapeseed oil, sesame oil, palmkernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil,tallow, soyabean oil, peanut oil, castor oil, seal oils, whale oil,shark oil, and other fish oils, teaseed oil, partially or completely hydrogenated animal and vegetable oils, such as those mentioned; hydroxyand alphahydroxy higher carboxylic, aliphatic and fatty acids, such asdihydroxystearic acid, dihydroxy palmitic acid, dihydroxy-behenic acid,alphahydroxy capric acid, alphahydroxystearic acid,alphahydroxy-palmitic acid, alphahydroxy lauric acid, alphahydroxymyristic acid, alphahydroxy cocoanut oil mixed fatty acids, alphahydroxymargaric acid, alphahydroxy arachidic acid, and the like; fatty andsimilar acids derived from various waxes, such as beeswax, spermaceti,montan wax, Japan wax, coccerin, and carnauba wax.

Such acids include carnaubic acid, cerotic acid,

molecular weight carboxylic acids derived, by oxidation and othermethods, from paraflin wax, petroleum and similar hydrocarbons; resinicand hydroaromatic acids, such as .hexahydrobenzoic acid, hydrogenatednaphthoic, hydrogenated carboxy diphenyl, naphthenic, and abietic acid;aralkyl and aromatic acids, such as benzoic acid,

Twitcheli fatty acids, naphthoic acid, carboxydiphenyl, pyridinecarboxylic acid, hydroxybenzoic acid, and the like.

Other suitable acids include phenylstearic acid, benzoylnonylic acid,campholic acid, fencholic acid, cctyloxybutyric acid, cetyloxyaceticacid, chlorstearic acid, etc.

It is also well known that diamines, and particularly those havingpronounced basic properties, may be derived by various means, providedthat the resultant diamine is characterized by the fact that the twoamino nitrogen atoms are not attached to the same carbon atom. Suchdiamines, generally referred to as alkylene diamines, are well known andmay be characterized by ethylene diamine. Derivatives of the diaminesherein contemplated are characterized by being a methylene diaminederivative, i. e., a derivative of the hypothetical methylene diMethylene diamine is almost unknown for practical purposes, since it isvery unstable in the form. of a free base, but does exist in the formatalkylated or acylated derivatives. In view of this fact, it becomesobvious that the new chemical compound or composition of matterpreviously.

referred to must necessarily be obtained indirectly, insofar that theparent diamine is almost non-existent.

It is well known that a large number of secondary amines are availablewhich-may be designated by the formula type:

BI! in which B represents an alkyl, aralkyl, alicyclic,

aryl, alkylol, aralkylol, hydroxy alicyclic, heterocyclic, or otherequivalent radical; and B" an alkylol, aralkylol, hydroxy alicyclic, orsimilar radical. Similarly, the formula f HN B represents a secondaryamine, in which a hydroxy hydrocarbon radical may or may not be presentasses H B/ B, The amine so produced may be indicated b the iollowinsformula:

in which, as has been previously pointed out, T may represent a hydrogenatom derived from rormaldehyde, or may represent a radical derived fromacetaldehyde, propiouaidehydc, butyraldehyde, heptaldehyde, lauricaldehyde, palmitic aldehyde, or stearic aldehyde, etc. Naturally, B"less than three times. Similarly, instead of aliphatic aldehydes, onemay employ heterocyclic aldehydes, such as lurfuraldehyde, or aromaticaldehydes, such as benzaldehyde. One may also employ alicyclicaldehydes, such as hexahydrobenzaldehyde. Unsaturated aldehydes, such asacrolein, crotonaldehyde, or tiglic aldehyde, may be e ployed. Aspreviously indicated, B may represent radicals, such as methyl, ethyl,propyl, butyl, amyl, hexyl, octyl, decyl, hexadecyl, octadecyl, orsimilar radicals. Similarly, B may rep resent an alkyl radical, such asa benzyl radical, ethyl benzyl radical, dimethyl benzyl radical, analicyclic radical, such as the cyclohexyl, methyl cyclohexyl, etc.;likewise, B, as well as B", may represent the radicals hydroxy ethyl,hydroxy propyl, hydroxy butyl, and other similar radicals, including aCeHrCaI-LOH radical, or, a CsHroOH radical. Other radicals include theiurfural radical, or hydroxy derivatives thereof. Piperidine may beconsidered as a special adaptation, in which one radical replaces twoamino hydrogen atoms. As previously indicated, B may be selected fromany of the type of radicals above mentioned; whereas, 13" is limited tothose radicals in which there is an alcoholic hydroxy group present,such as an alkylol radical, etc.

It is to be noted that the methylene diamine, expressed by the aboveformula, is a tertiary diamine in the sense that neither amino nitrogenatom has attached thereto a replaceable hydrogen atom. For convenience,the above formula may be rewritten as follows, so as to indicate thatthere is present an alcoholic hydrorryl radcal:

in which B'."OH is obviously the monovalent hydroxy hydrocarbon radical,such as an alkylol radical or the like. It is well known that amines,particularly non-aryl, such as triethanolamine or the like, can beacylated by reaction with fatty acids, or a suitable functionalde'rivativethereot, such as the acyl chloride, or the anhydride, or eventhe ester. It the tertiary hydroxymethylene diamine or the kind justdescribed is reacted with a detergent-forming monobaslc car-boxy acid,the reaction may be indicated in the following manner:

with the formation of an intermediate ester, which may be indicated inthe following manner:

a'moooa B An examination 0! the previous formulas remay occur more thanonce, and B" the hydroxylated amine and onemole of the veals that thehydroxylated tertiary acylated methylene diamine must contain at leastone hydroxyl, and might contain as many as nine hydroxyls available foresterification; and as a matter of fact, might contain an even greaternumber if, instead of using the secondary amine, such as diethanolamine,dipropanolamine, dibutanolamine, etc., one employedethanolglycerylamine, propyl glycerylamine, or diglycerylamine.

' Amines derived from diglycerol, instead of glycerol, would furnishradicals containing three hydroxyls, even after attachment to the aminonitrogen atom. If, in all instances, B and B' are derived fromdiglycerylamine, there would be present at least sixteen hydroxyls, andthere might be present at least one more if aldol or a higher homologuewere employedas a reactant in formation of the intermediate ester.

In addition to aldol, other similar hydroxy' aldehydes oraldehyde-alcohols may be employed. As to such aldehydes other thanaldol, reference is made to Richters Organic Chemistry," (Allott),volume. 1, Third English Edition, 1934, pages 389-391. g

In view of what has been said previously, it does not appear necessaryto enumerate various suitable amines which may be employed for reactionwith a selected aldehyde, but it may be well to indicate that amongthose which may be employed are the following: diethanolamine,dipropanolamine, dibutanolamine, dioctanolamine, dipentanolamine,glycerol hexanolamine, methyl glycerylamine, ethyl glycerylamine, propylglycerylamine, cyclohexyl glycerylamine, benzyl glycerylamine;dibenzylamine, ethyl benzy-lamine, methyl benzylamine, propylbenzylamine, phenolmohoethanolamine, naphthylmonoethanolamine,cyclohexyl ethylamine, cyclohexyl propylamine, cyclohexyl hexylamine,diethyla mine, dipropylamine, diamylamine, dihexylamine, dioctylamine,diglycerylamine, etc. In all the previous examples each radicalindicates a substitute for an amino hydrogen atom. Similarly, amines canbe obtained from polyglycerols or polyglycols, as, for instance, thesecondary amines, indicated by the following formulas:

CZHAOCIHlOH iHlOCzHlOH CIHAOH CIHGOCIHOH I 01H: Such amines may serve asfunctional equivalents of the previously described amines, which happento be free from an ether linkage. Likewise, one may have amines in whichthere is more than one ether linkage, i. e., in which the hydrocarbonradical which replaces an amino hydrogen atom has been interrupted morethan once by an oxygen atom.

In examining the previous formulas, it be-' comes evident that if twodiflerent amines are employed, one of which does not contain ahydroxylated hydrocarbon radical, then the reac-. tion is not limited totwo dissimilar amines, but may take place in part in such a manner as toinvolve two similar amines, i. e., the aldehyde may react with twomolecules of the hydroxylated amine; it may react with one mole ofnon-hydroxylated amine: or it may be united with two moles of thenon-hydroxylated amine. In such event, as last mentioned, the resultantcompound is without value, unless a hydroxy aldehyde, such as aldol, hasbeen employed. In such event an attempt to esterify with adetergent-monocarboxy acid, or the like, results in the'formation of anentirely difierent type of material, i. e., an acid radical beingintroduced into the aldehyde radical or residue, as difieren-' tiatedfrom the amine radical residue. For practical purposes, then, it is mostexpedient to manufacture or produce a methylene diamine from a singlekind of secondary amine; and in such event, obviously it must be ahydroxylated amine, such as diethanolamine, except if one uses aldol orthe like. In subsequent examples, diethanolamine is employed as thesecondary amine for reaction with the aldehyde; but in view of what hasbeen said previously, various other secondary amines or mixtures thereofmight be employed.

Attention is again directed to the fact that wherever a hydroxyl radicalexists, and provided it is not necessary for subsequent reaction, thensuch hydroxyl radical could be reacted with an acid, such as aceticacid, butyric acid, heptoic acid, etc.; and this statement applies tothe hydroxyl radical of an alcohol aldehyde, such as aldol. Furthermore,an alkylol radical might be so combined as has been previously pointedout, or the alcohol radical or its equivalent might be combined with amonohydric alcohol. In essence, such combination simply results in thehydrocarbon chain interrupted at least once by an oxygen atom, asdifferentiated from an uninterrupted hydrocarbon chain. In the heretoappended claims reference to an alkyl, alkylol, or similar radical isintended specifically to include such examples where there isinterruption of the chain or ring by an oxygen atom.

Having obtained the hydroxylated tertiary methylene diamine of the kinddescribed in an anhydrous state or approximately anhydrous state, thenext step is to obtain acylation by means of a high molal carboxy acid,and more particularly, a detergent-forming acid. Such procedure iscomparable to the type of reaction in which other well knownhydroxylated amines are esterified, i. e., made or caused to act like analcohol. For instance, it is comparable to the reaction by which a fattyacid radical, such as the ricinoleic acid radical is introduced into ahydroxylated tertiary amine. The same procedure is employed, forexample, in introducing a high molal carboxy acid radical into acompound, such as tetrahydroxyethyl ethylene diamine or triethanolamine. See U. S Patents Nos. 2,167,347 and 2,167,348, to De Groote.Keiser and Blair, issued July 25, 1939.

Briefly stated, the method of producing such reactions is as follows:The acid, particularly a Instead of the acid itself, obvious functionalequivalents, such as the anhydride, the acyl chloride, an ester, or anamide may be employed. The entire object is to use a compound which hasa labile acyl group, or to state the matter tions'to the use of acylchloride, in that one ob tains the salt of the compound, i. e., the acidchloride, which may not be as desirable as the unneutralized base. Themass may be heated during the reaction'period, and the reaction periodmay vary from 2-8 hours. If desired, an inert gas such as nitrogen maybe passed through the mixture while being reacted.

Our preferred reagent is obtained in the following manner:

We react a readily available aldehyde, such as acetaldehyde orheptaldehyde, in the molecular proportions of one mole of aldehyde withtwo moles of diethanolamine. Such reaction is conducted in the mannerpreviously noted; and after completion of reaction, any water stillpresent which has not been removed previously in .the course ofreaction, is removed by distillation, preferably under vacuum.

A Such hydroxylated diamlne is then treated in th proportion of threemoles of diamlne to two moles of castor oil, which consists essentiallyoi triricinolein. Any suitable quantity of material may be employed, forinstance, 500 lbs. of the selected anhydrous diamine and the appropriateamount of. castor oil. The two products are mixed together and heated ata. reasonable temperature above the boiling point of water and below thepoint of decomposition, for instance, at some temperature between135-195 C. for a suitable period of time, i. e., 1 to 5 hours. Constantstirring may be employed, if desired. Also one may pass dried nitrogengas through the reaction mass. The product so obtained is the acylateddiamlne mixed with some free glyceroland certain other accompanyingcogeneric products.

It is to be noted that the compounds described are basic in character,due to the presence 01 an unacylated basic amino nitrogen atom, or dueto th presence of an esterifled group of the kind described. In suchinstances'the compound may be employed as such, or may be employed inbasic form, (i. e. after combination with water), or

may be employed in salt form by reaction with an acid, such as aceticacid, lactic acid, hydrochloric acid, or any other suitable acid.

It is to be noted that the procedure previously described can beemployed to introduce one or more acyl radicals into a hydroxylatedtertiary methylene diamlne or the kind described. The introduction ofmore than one acyl radical, of course, obtained from a high molecularweight carboxy acid or the like is predicated on the presence of morethan one alcoholic hydroigvl radical. Obviously. the product obtained inthe manner described in preparation of thepreierred reagent would yielda product containing our hydroxyl radicals. It is our preference tointromore than two. The most desirable reagents are those which areobtained by the introduction of a single acyl radical derived from ahigh molecular weight carboxy acid, and more particularly, from thedetergent type acid. The fatty acids yield the most desirable compounds,and ricinoleic acid represents the most desirable compounds, andricinoleic acid represents the most desirable type of fatty acid. It hasbeen previously pointed out that the amino nitrogen atoms present are inbasic form, and that either one or both nitrogen atoms may be combinedwith water or a suitable acid; or the compounds can be employed inuncombined form, i. e., in the form of a free base.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

,1. A methylene diamlne ester of the formula:

in which R4 is selected from the class consisting alkylene radicals inwhich the carbon atom chain has been interrupted at least once byoxygen;

. RCOO is the acyloxy radical of a high molecular weight carboxy acidhaving more than 6 and less than 40 carbon atoms; and R2 is a radicalselected from the class consisting of alkyl, aralkyl, alicyclic, aryl,alkylol, aralkylol, hydroxyalicyclic,

alkylol-ether, polyhdroxylated alkyl, and polyhydroxylated alkyl-ether,and RCOORs radicals and in said last mentioned RCOOR's radicals, R5 andR000 have their prior significance.

2. A methylene diamlne ester of the formula:

in which R4 is selected from the class consisting of hydrogen atoms andhydrocarbon radicals having not over 18 carbon atoms; RCOOR5 is aradical in which R5 is a divalent radical selected from the class ofalkylene radicals, alkylene radicals in which the carbon atom chain hasbeen interrupted at least once by an oxygen atom, hydroxyalkyleneradicals, and hydroxylated alkylene radicals in which the carbon atomchain has been interrupted at least once by oxygen; RCOO is the acyloxyradical oi! a detergent-forming monocarboxy acid having more than 6 andless than 40 carbon atoms; and R2 is a radical selected from the classconsisting of alkyl, aralkyl, alicycllc, aryl, alkylol,aralkyloL'hydroxy alicyclic, alkylol-ether, polyhydroxylated alkyl, andpolyhydroxylated alkyl ether, and RCOORc radicals and in said lastmentioned RCOORs radicals, R5 and'RCOO have their prior significance.

3. A methylene diamlne ester 01 the formula:

having not over 18 carbon atoms; RCOORc is a duce at least oneacylradical, and preferably, not 73 radical in which R: is a divalentradical selected from the class of alkylene radicals, alkylene-radicalsin which the carbon atom chain has been interrupted at least once by anoxygen atom, hydroxyalkylene radicals, and hydroxylated 6. A methylenediamine ester of the formula:

RCOORs R4 R1 BCOOR; n R:

4. A methylene diamine ester of the formula:

RCOORE R4 R:

N--CN l RCOOR; H R:

in which R4 is selected from the class consisting of hydrogen atoms andhydrocarbon radicals having not over 18 carbon atoms; RCOOR: is aradical in which R5 is a divalent radical selected from the class ofalkylene radicals, alkylene radicals in which the carbon atom chain hasbeen interrupted at least once by an oxygen atom, hydroxyalkyleneradicals, and hydroxylated alkylene radicals in which the carbon atomchain has been interrupted at least once by oxygen; RCOO is the acyloxyradical of a higher-fatty acid having 18 carbon atoms; and R2 is aradical selected from the class consisting of alkyl, aralkyl, alicyclic,aryl, alkylol, aralkylol, hydroxyalicyclic, alkylolether,polyhydroxylated alkyl, and poyhydroxylated alkyl-ether, andRCOORsradicals and in said last mentioned RCOORs radicals, R5 and R000have their prior significance.

5. A methylene diamine ester of the formula:

in which R4 is selected from the class consisting of hydrogen atoms andhydrocarbon radicals, having not over 18 carbon atoms; RCOORs is aradical in which R5 is a divalent radical selected from the class ofalkylene radicals, alkylene radicals in which the carbon atom chain hasbeen interrupted at least once by an oxygen atom, hydroxyalkyleneradicals, and hydroxylated alkylene radicals in which the carbon atomchain has been interrupted at least once by oxygen;

RCOO is the acyloxy radical of a higher unsaturated fatty acid having 18carbon atoms: and R2 is a radical selected from the class consisting ofalkyl, aralkyl, alicyclic, aryl, alkylol, aralkylol,

hydroxyalicyclic, akylol-ether, polyhydroxylated in whichRi is selectedfrom the class consisting I of hydrogen atoms and hydrocarbon radicalshaving not over 18 carbon atoms; RCOORs is a radical in which R5 is adivalent radical selected from the class of alkylene radicals, alkyleneradicals in which the carbon atom chain has been interrupted at leastonce by an oxygen atom, hydroxyalkylene radicals, and hydroxylatedalkylene radicals in which the carbon atom chain 16 has been interruptedat least once by oxygen; RCOO is the ricinoleyloxy radical; and R2 is aradical selected from the class consisting of alkyl, aralkyl, alicyclic,aryl, alkylol,aralkylol, hydroxyalicyclic, alkylol-ether,polyhydroxylated alkyl, and polyhydroxylated alkyl-ether, and RCOORsradicals and in said last mentioned RCOOR5 radicals, R11; and R000 havetheir prior significance,

7. A methylene diamine ester of the formula:

11.00001?! R4 CzH OH in which Rris selected from the class consisting ofhydrogen atoms and hydrocarbon radicals having not over 18 carbon atoms,and RCOO is the ricinoleyloxy radical.

8. A methylene diamine .ester of the formula:

12.000011! R. canon N- -N I acoocnz. H cimon in which R4 is selectedfrom the class consisting of hydrogen atoms and hydrocarbon radicalshaving not over 18 carbon atoms, and R000 is .the ricinoleyloxy radical.

9. A methylene diamine ester of the formula:

n.'cooc,m a. cnnoocn' N- acoocim H canon in which R4 is selected fromthe class consisting of hydrogen atoms and hydrocarbon radicals havingnot over 18 carbon atoms, and RCOO is the ricinoleyloxy radical.

10. A method for manufacturing the methylene diamine esters defined inclaim 1, which consists in reacting a high molecular weight carboxy 65acid having more than 6 and less than 40 carbon diamine in which atleast one amino hydrogen atom has been replaced by a member of the classconsisting of alkylol, aralkylol, hydroxy- -alicyclic, alkylol-ether,polyhydroxylated alkyl, and polyhydroxyl alkyl-ether radicals.

MELVIN DE GROOTE. BERNHARD KEISER.

atoms, with a hydroxylated di-tertiary methylene

